Ether triester derivatives of p-dioxanone

ABSTRACT

wherein R is alkyl of from 1 to 7 carbon atoms and X is an alkyl of 2 to 8 carbon atoms or -CH2CH2 nOn 1 where n is an integer of from 2 to 4. These novel compounds are produced by reacting pdioxanone with a glycol having from 2 to 8 carbon atoms or a glycol derived from the addition of ethylene oxide to ethylene glycol and esterifying the reaction product with a carboxylic acid having from 2 to 8 carbon atoms or a corresponding acid anhydride. These ether-triesters are particularly useful as plasticizers for polyvinyl chloride.   This invention relates to a new series of ether-triester derivatives of p-dioxanone having the formula

United States Patent [1 1 Snapp, Jr. et al.

[ 1 Dec. 30, 1975 [54] ETHER TRIESTER DERIVATIVES OF P-DIOXANONE [75]Inventors: Thomas C. Snapp, Jr.; Alden E.

Blood, both of Longview, Tex.

[52] U.S. Cl. 260/410.6; 260/476; 260/484 A [51] Int. Cl. C09F 5/08 [58]Field of Search 260/410. 6, 484 A, 476

[56] References Cited UNITED STATES PATENTS 2,962,455 11/1960 Hostettler..260/484A 3,000,747 9/1961 Martin 260/484 A 3,086,044 4/1963Kerschner.... 260/484 A 3,689,531 9/1972 Critchfield... 260/484 A3,767,627 10/1973 Schoen 260/484 A [57] ABSTRACT This invention relatesto a new series of ether-triester derivatives of p-dioxanone having theformula wherein R is alkyl of from 1 to 7 carbon atoms and X is an alkylof 2 to 8 carbon atoms or CH CH ,,O,, where n is an integer of from 2 to4. These novel compounds are produced by reacting p-dioxanone with aglycol having from 2 to 8 carbon atoms or a glycol derived from theaddition of ethylene oxide to ethylene glycol and esterifying thereaction product with a carboxylic acid having from 2 to 8 carbon atomsor a corresponding acid anhydride. These ethertriesters are particularlyuseful as plasticizers for polyvinyl chloride.

lilClaims, No Drawings ETHER TRIESTER DERIVATIVES OF P-DIOXANONE Thisinvention relates to a new family of chemical compounds, namelyether-triester derivatives of pdioxanone. The new compounds have thefollowing structural formula:

wherein R is alkyl of from 1 to 7 carbon atoms and X is an alkyl of 2 to8 carbon atoms or (-Cl-l Cl-l ,O,, where n is an integer of from 2 to 4.

The novel ether-triesters described herein result from the selectivereaction of p-dioxan-2-one (p-dioxanone) with various glycols to yieldan intermediate hydroxylated ether-ester which can then be esterified.The highly selective reaction of p-dioxanone with a glycol wasunexpected, since transesterification of the hydroxy ether-ester productwith p-dioxanone could readily occur and p-dioxanone self-condensationwould be a predicted side reaction. Neither the transesterification northe self-condensation reaction was encountered in the synthesis of theether-triesters.

The novel ether-triesters of this invention exhibit good utility in abroad range of applications. They have been found to be particularlyeffective plasticizers for polyvinyl chloride resin. The plasticizerproperties of these compounds are characterized by good volatility andlow temperature flexibility. Other application areas in which thesecompounds are useful include viscosity improvers for motor oil and brakefluid; and solvents in waxes, polishes and lubricants.

The novel ether-triesters are prepared by a two-step reaction sequence.It is believed that the reaction proceeds according to the followingequations:

etc.) and N,N-dialkylanilines, alkali metal hydroxides and alkalineearth oxides. However, the desired prodnot can be produced in anoncatalyzed reaction between the two reactants. lf catalysts are used,a catalyst concentration of from about 0.01 to about 2.0 weight percent,based on the total reactant weight, should be employed. The reactiontemperature at this stage should be from about C. to about 150C. Thereaction can be conducted at a greater than atmospheric pressure withoutdetrimental effects to the product. A mole ratio of glycol to lactonecan be from about 1:1 to about 10:1, respectively. A preferred ratio ofreactants is from about 1:1 to about 3:1, respectively.

Novel ether-triesters are produced by esterification of hydroxyalkylB-hydroxy ethoxy acetates with a carboxylic acid of acid anhydride. Thecarboxylic acid or anhydride is aliphatic or aromatic in nature with acarbon chain of from 2 to 8 carbon atoms. Suitable acids or acidanhydrides for this esterification are acetic, propionic, butyric,isobutyric, pentanoic, 2- methylpentanoic, hexanoic, 2-ethylhexanoic,benzoic and toluic acid. The mole ratio of hydroxylated ester to acidmoiety should be from about l.O:2.0 to about 1.0125, respectively, toinsure complete esterification of the dioletherester.

Esteriflcation with an anhydride is achieved with or without catalysisat temperatures of from about 50C.

to about 200C. However, esterification with the carboxylic acid isenhanced by a low concentration (from about 0.01 to about 1.0 weightpercent based on total weight of the reactant) of acid catalyst toproduce the desired diester product. Suitable acid catalysts aresulfuric acid, p-toluenesulfonic acid, hydrochloric acid, phosphoricacid, methanesulfonic acid, and zinc chloride. An azeotropic agent suchas benzene, toluene, xylene, or hexane is useful to aid water removalduring the reaction.

The novel ether-triesters are viscous, colorless liquids or low meltingsolids which can be distilled at reduced In the first step, an aliphaticglycol is reacted with pdioxanone to produce thehydroxyalkyl-B-hydroxyethoxy acetate-In the secondstep of the reaction,the dihydroxylated product is esterifled to give the noveltriester-ethers.

The aliphatic glycols which can be used in this invention are diolshaving 2 to 8 carbon atoms or glycols derived from ethylene oxide inaddition to ethylene glycol. Suitable glycols for this invention includeethylcne glycol, neopentyl glycol, propylene glycol, 1,4- butanediol,butylene glycol, l,6-hexanediol and and 2,3-hexanediol. Suitablepolymethylene glycols include diethylene, triethylcne and tetraethylene.This reaction is accomplished with an acid or basic catalyst toaccelerate the reaction rate. Suitable catalysts for this reaction aresulfuric acid, organotin compounds (dibutyltin oxide, dibutyltindilaurate, etc.), hydrochloric acid, zinc chloride, p-toluenesulfonicacid, pyridine, aliphatic tertiary amines (triethylarnine',tributylamine,

EXAMPLE 1 This example shows the synthesis of an ether-triester byreaction of p-dioxanone with a glycol to yield a dioletherester which isesterified to the:desired product. In this example a l-liter, four-neckflask is fitted with a stirrer, dropping funnel, thermometer andcondenser with an attached nitrogen blanket. The flask is charged with124 grams (2.0 moles) of ethylene glycol and heated to 100C. Freshlydistilled p-dioxanone (204 grams, 2.0 moles) is slowly added over a 30-minute period. After the addition is complete. the reaction mixture isstirred for 6 hours. To the resulting mixture at 100C. is added 459grams (4.5 moles) of acetic anhydride during a one hour period. Completeesterification is accomplished by heating for 6 hours at 10 100C.Fractional distillation at reduced pressure affords the ether-triesterwhich is a colorless, viscous liquid distilling at 128130C. at 0.5 mm.mercury pressure in an 85 percent yield. Saponification equivalentanalysis is 81.1 (theoretical is 82.7). Infrared specl5 troscopyverifies the ether-triester structure.

cal oca c H2OCH2HOCH2CH2OHCH3 EXAMPLE 2 This example demonstrates thesynthesis of an ethertriester by reaction of p-dioxanone with a glycolto yield a dioletherester which is esterified with an acid Reflux ofthis mixture at 125C. gives milliliters of water. The resulting solutionis submitted to fractional distillation to give an 85 percent yield of acolorless, viscous liquid. Saponification equivalent analysis of theproduct is 128.7 (theoretical for the ether-triester is 130.7).

Infrared and nuclear magnetic resonance spectroscopy verifies thesynthesis of the ether-triester.

EXAMPLE 4 anhydride. The procedure in Example 1 is followed. A mixtureof 90 grams (1 mole) of 1,4-butanediol and 1 gram of pyridine is reactedwith 102 grams (1 mole) of 3 EXAMPLE 3 EXAMPLE 5 The procedure inExample 1 is followed with 76 grams 1.0 mole) of propylene glycolreacting with 102 grams (1.0 mole) of p-dioxanone containing 0.5 gram ofp-toluenesulfonic acid catalyst at 125C. for 4 hours. The resultingproduct is mixed with 317 grams (2.2 moles) of Z-ethylhexanoic acid and30 milliliters of toluene. Refluxing of this mixture at 140C. gives theether-triester with the removal of 36 milliliters of water. Theresulting mixture is submitted to fractional distillation to give acolorless. viscous liquid having a saponification equivalent analysis of145.2 (theoretical is 143.3). lnfrared and nuclear magnetic resonancespectroscopy verifies the ether-triester synthesis.

CH H

The procedure in Example 1 is followed with grams (1.0 mole) of1.4-butanediol reacting with 102 This example describes the synthesis ofan ether-tri- 60 grams (1.0 mole) of p-dioxanone containing 0.5 gramester by reaction of p-dioxanone with an ether glycol to yield adioletherester which is esterified to the desired product. The procedurein Example 1 is followed. A mixture of 150 grams (1.0 mole) oftriethylene glycol and one gram of tributylamine is reacted with 102grams 1.0 mole) of p-dioxanone at C. for 6 hours. Catalyst is removed byheating at 100C. under reduced pressure. This reaction product is mixedwith 216 grams (2.2 moles) of isobutyric acid and 1 gram ofp-toluenesultonic acid with 50 milliliters of toluene.

of p-toluenesulfonic acid catalyst at C. for 4 hours. The resultingproduct is mixed with 256 grams (2.1 moles) of benzoic acid and 30milliliters of toluene. Refluxing of this mixture at C. gives theether-triester with the removal of 36 milliliters of water. Theresulting mixture is submitted to fractional distillation to give acolorless, viscous liquid having a saponification equivalent analysis of135.9 (theoretical is 133.3). infrared and nuclear magnetic resonancespectroscopy verifies the ether-triester synthesis.

but it will be understood that variations and modifical tions can beeffected within the spirit and scope of the invention as describedhereinabove.

We claim:

1. A compound having the formula wherein R is alkyl of from 1 to 7carbon atoms and X is an alkyl of 2 to 8 carbon atoms or -(-Cl-l CH ,O,,where n is an integer of from 2 to 4.

2. The ether-triester in claim 1 wherein X is alkyl with 2 carbon atomsand R CH 3. The ether-triester in claim 1 wherein X is alkyl with 4carbon atoms and R C l-l 4. The cther-triester in claim 1 wherein X isalkyl with 3 carbon atoms and R C-,H,

5. The ether-triester in claim 1 wherein X is Cl-l CH ),,O,, with n as 2and R -C H 6. The ether-triester in claim 1 wherein X is CH CH ),,O,,with n as 3 and R is phenyl.

7. A process for the production of ether-triesters having the formulawherein R is alkyl of from 1 to 7 carbon atoms and X is an alkyl of 2 to8 carbon atoms or -(-CH CH O,, where n is an integer of from 2 to 4,which comprises reacting p-dioxanone with an aliphatic glycol havingfrom 2 to 8 carbon atoms or a glycol derived from the addition ofethylene oxide to ethylene glycol and subsequently esterifying thereaction product with an aliphatic carboxylic acid having from 2 to 8carbon atoms or an anhydride thereof.

8. A process according to claim 7 wherein the glycol is selected fromthe group consisting of ethylene glycol, neopentyl glycol, propyleneglycol, l,4-butanediol, butylene glycol, 1,6-hexanediol, 2,3-hexanediol,dieth ylene glycol, triethylene glycol and tetracthylene 9. A processaccording to claim 7 wherein the reaction of the p-dioxanone and theglycol is conducted in the presence of a catalyst.

10. A reaction according to claim 9 wherein the acid or base catalyst isselected from the group consisting of sulfuric acid, organotin compoundshydrochloric acid, zinc chloride, p-toluenesulfonic acid, pyridine,aliphatic tertiary amines, N,N-dialkylanilines, alkali metal 4hydroxides and alkaline earth metal oxides.

11. A reaction according to claim 9 wherein the catalyst is present in aconcentration of from about 0.01 percent to about 2.0 percent based uponthe total weight of the reactant.

12. A process according to claim 7 wherein the reaction of p-dioxanoneand glycol is conducted at a temperature of from about 50C. to aboutl50C.

13. A process according to claim 7 wherein the mole ratio of alcohol top-dioxanone is from about 1:1 to about 10:1, respectively.

14. A process according to claim 13 wherein the mole ratio of alcohol top-dioxanone is from about 1:1 to about 3:1, respectively.

15. A process according to claim 7 wherein the esterification reactionis conducted with a carboxylic acid or acid anhydride thereof selectedfrom the group consisting of acetic, propionic, butyric,Z-methylpentanoic, hexanoic, 2-ethylhexanoic, octanoic, benzoic, ortoluic acid.

16. A process according to claim 15 wherein the esterification isconducted in the presence of a catalyst selected from the groupconsisting of sulfuric acid, p-toluenesulfonic acid, methanesulfonicacid, hydrochloric acid, phosphoric acid or zinc chloride.

17. A process according to claim 16 wherein the esterification catalystis present in an amount of from about 0.01 weight percent to about 2.0weight percent based upon the total weight of the reactants.

18. A process according to claim 15 wherein the esterification with analiphatic carboxylic acid or acid anhydride thereof is conducted at atemperature of from about C. to about 200C.

19. A process according to claim 7 wherein the mole ratio ofintermediate hydroxylated ester to acid moiety is from about 1:2 toabout 1:25, respectively.

P(%-/%5)0 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION pawnt3,929,846 Dated December 30, 1975 Inventor) Thomas C. Snapp, Jr. AldenE. Blood It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

Column 5, line 29, delete "-CH CH O and insert therefor 2 2 n n-l (CH CHO n H Column 5, llne 31, delete CI- I CH 0 and lnsert therefor Column 6,line 4, after "tetraethylene" insert -glycol.--.

Column 6, line 10, insert a comma after "organotin compounds".

Signed and Scaled this sixteenth Day Of March 1976 [SEAL] Attest:

RUTH C. MASON C. MARSHALL DANN 14119811718 11 Commissioner uflqrents andTrademarks

1. A COMPOUND HAVING THE FORMULA
 2. The ether-triester in claim 1wherein X is alkyl with 2 carbon atoms and R CH3.
 3. The ether-triesterin claim 1 wherein X is alkyl with 4 carbon atoms and R -C4H9.
 4. Theether-triester in claim 1 wherein X is alkyl with 3 carbon atoms and R-C7H15.
 5. The ether-triester in claim 1 wherein X is -CH2CH2)nOn 1 withn as 2 and R -C7H15.
 6. The ether-triester in claim 1 wherein X is-CH2CH2)nOn 1 with n as 3 and R is phenyl.
 7. A process for theproduction of ether-triesters having the formula
 8. A process accordingto claim 7 wherein the glycol is selected from the group consisting ofethylene glycol, neopentyl glycol, propylene glycol, 1,4-butanediol,butylene glycol, 1,6-hexanediol, 2,3-hexanediol, diethylene glycol,triethylene glycol and tetraethylene
 9. A process according to claim 7wherein the reaction of the p-dioxanone and the glycol is conducted inthe presence of a catalyst.
 10. A reaction according to claim 9 whereinthe acid or base catalyst is selected from the group consisting ofsulfuric acid, organotin compounds hydrochloric acid, zinc chloride,p-toluenesulfonic acid, pyridine, aliphatic tertiary amines,N,N-dialkylanilines, alkali metal hydroxides and alkaline earth metaloxides.
 11. A reaction according to claim 9 wherein the catalyst ispresent in a concentration of from about 0.01 percent to about 2.0percent based upon the total weight of the reactant.
 12. A processaccording to claim 7 wherein the reaction of p-dioxanone and glycol isconducted at a temperature of from about 50*C. to about 150*C.
 13. Aprocess according to claim 7 wherein the mole ratio of alcohol top-dioxanone is from about 1:1 to about 10:1, respectively.
 14. A processaccording to claim 13 wherein the mole ratio of alcohol to p-dioxanoneis from about 1:1 to about 3:1, respectively.
 15. A process according toclaim 7 wherein the esterification reaction is conducted with acarboxylic acid or acid anhydride thereof selected from the groupconsisting of acetic, propionic, butyric, 2-methylpentanoic, hexanoic,2-ethylhexanoic, octanoic, benzoic, or toluic acid.
 16. A processaccording to claim 15 wherein the esterification is conducted in thepresence of a catalyst selected from the group consisting of sulfuricacid, p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid,phosphoric acid or zinc chloride.
 17. A process according to claim 16wherein the esterification catalyst is present in an amount of fromabout 0.01 weight percent to about 2.0 weight percent based upon thetotal weight of the reactants.
 18. A process according to claim 15wherein the esterification with an aliphatic carboxylic acid or acidanhydride thereof is conducted at a temperature of from about 75*C. toabout 200*C.
 19. A process according to claim 7 wherein the mole ratioof intermediate hydroxylated ester to acid moiety is from about 1:2 toabout 1:2.5, respectively.